Polycarboxylates



POLYCARBOXYLATES Joachim Dazzi, Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application January 19, 1953 Serial No. 332,119

8 Claims. (Cl. ZED-404.8)

The present invention relates to adducts and more particularly provides new polycarboxylates, methods of preparing the same by the addition reaction of certain tuma' rates with certain esters of acylricinoleic acids, and vinyl chloride. polymers plasticized .with :the new :polycarboxylates.

According to the invention there areprovided addition products having the formula:

in which R, R, Y and Y? are alkyl radicals of from 1m carbon atoms, X is a mono-alkenyl radical of 10 carbon atoms, and n is an integer-of from 1 to.3.

Polycarboxylates having the above formula, may be readily prepared by contacting an .acylated ricinoleate having the vformula:

onaonnacn;onionzcrttonmoo0n in which R and R areras above defined, with adialkyl fumarate of from 6 to 14 carbon atoms.

Useful acylated ricinoleates include the methyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or n-amyl esters of such acylated ricinoleic acids as l2-acetoxy-9-oc,tadecenoic acid, 12-propionyloxy-9-octadecenoic acid,' and l2-n-butyryloXy-9-octadecenoic acid. The us fulacyl ated ricinoleates are known compounds which are readily avaitable by reaction of an appropriate alkyl .ricinoleate with a suitable acid, acid halide, or acid anhydride.

Alkyl fumarates which are condensed with the above acylated ricinoleates are the simple diesters such as methyl, amyl, ethyl, n-propyl ortisobutyl fumarate and the mixed esters such .as ethyl isopropyl fumarate, isobutyl methyl fumarate or ethyl methyl fumarate.

Reaction of the acyl-ated ricinoleates with the furnarate is eifected by simply heating a mixture of .the two reactants at temperatures of from, say, 100 C; to 300 0., depending upon the nature of the individual reactants and of the properties desired in :the final products The reaction is generally effected at atmospheric pressure, but pressures below atmospheric orabove atmospheric may be used. Condensationtcatalysts may bev employed. The reaction results in the addition of from 1 to 3 moles of the fumarate at the alkenyl portion of the rieinoleate. Thus the reaction of a simpledialkyl fumarate such as methyl fumarate with an ester like methyl acetylricinoleate can yield adducts in which from 1 to 3 moles of the furnarate have reacted with the ricinoleate, depending aired States Patent 0 moo 00 em 00 cm lOHtC 0.0 CH3 in which n is an integer of from 1 to 3 and X is a monoalkenyl chain of 10 'carbonatoms.

The present adducts are stable, high-boiling, clear and substantially colorless products which range from viscous-liquids to semi-solid masses. They may be advantageously employedfor a variety of industrialpurposes', e.- g.-, as lubricant additives, as intermediates for the production of'surface-activeagents,- etc. They are particularly valuable as plasticizers 'forvinyl chloride polymers, the present esters serving not only to-soften vinyl chloride polymers, but also to impart simultaneously a high degreeof'low temperature flexibility, very good-temperature stability and great mechanicalstrength to thesepolymers; They-arecompatibil'e with vinyl chloride polymers and show no-exudation of plasticizer evenat plasticizer content of up to 50 percent. Although the quantity of plasticizer will depend upon the particular polymer to be plasticized and-upon its molecular. weight, it is generally found that compositions having =from=5 p-ercentlby weight of plasticizer will, in most cases,.-be satisfactoryfor generalutility. The good flexibility-of-the 'plasticized compositions increases :with increasingplasticizer concentration.

The present polyoarboxylateszare valuable plasticizers for polyvinyl chloride and copolymers of at least 70 percent by weight of vinyl chloride and up to 30 percent by weight of. antunsaturated monomercopolymerizable therewith, forexample, vinylacetate,= vinylidene. chloride, etc.

In evaluating plasticizer etficiency, useis made of the following empirical testingprocedures:

Compatibility..Visua1 inspection of ,the plasticized composition is employed, incompatibility of the plasticizer with the polymer being demonstrated by cloudiness and exudation of, the plasticizer,

Hardness.A standard instrument made by the Shore Instrument and Manufacturing Company is used for this determination and expresses the hardness in units offrom l to 100. The hardness of a composition is judged by its resistance to-the penetration of standard needle applied to the composition under astandard load for a standard length of time.

Low temperature flexibility.--Low temperature flexibility is one of the most important properties of elastomeric vinylcompositions. While many plasticizers will produce flexible compositionsat room temperature, the flexibility .of' these compositions .at low temperatures, may vary considerably, i. e., plasticized polyvinyl chloride compositions that are flexible atroom temperatures often become very brittle and useless v atlow temperatures. Low temperatureflexibility ,testsherein employed are according to the Clash-Berg methoch, This method determines the torsional flexibility of a plastic at various temperatures. The temperature ,at ;which the vinyl composition exhibits an arbitrarily established minimumfiexibility is defined as the low temperature flexibility of the composition. This value-may also be definedas. the lower te m perature lirnitvof the plasticized .compositions usefulness as an elastomer.

Volatility..Just as a decrease in temperatureoften results indecreased flexibility vof fa plasticized polymer composition so does a decrease in plasticizer concentration when caused by volatilization of the plasticizer. Hence, plasticizers which are readily 'volatilized from the plasticized composition as a result of aging or heating 7 are ineflicient because upon volatilization the plasticized composition becomes stitf'andhardf The test for plasticizer volatility herein employed is the carbon absorption method of the Society of the Plastics Industry. 7

Water resistance.-The amountof water absorption and the amount'of leaching that takes place when the plasticized composition is immersed in distilled water for 24 'hours is determined.

The invention is further illustrated, but not limited, by the following examples:

Example 1 To a flask equipped with a reflux condenser and mechanical stirrer there were placed 116.3 g. (0.3 mole) of butyl acetylricinoleate and 205.2 g. (0.9 mole) of n-butyl fumarate, the mixture was brought to refluxing (260? C.) within 25 minutes and refluxed (252-260") for about 3 hours. Fractional distillation of the resulting reaction .rnixture gave 70.7 g. of a fraction, B. P. 120185 C./23

mm., n 1.4450, unreacted butyl fumarate; 46 g. of a fraction, B. P. 195-215 C./ 2 mm., 11 1.4526, probably unreacted butyl acetylricinoleate; and 198 g. of residue,

vrz l.4647, alight yellow viscous liquid. Based on the recovered reactants, the residue is a 1:3 molar ratio butyl acetylricinoleate-butyl fumarate adduct. It is identifie as adduct I in the plasticizer tests of Example 4. 1

V Exam'pleZ A mixture consisting of 69.2 g. (0.2 mole) of'methyl acetyl ricinoleate and 137 g. (0.6 mole) of butyl fumarate was heated at 245-260 C; for 1.5 hours. Distillation of the resulting reaction mixture in a nitrogen atmosphere gave 75.6 g. of. a fraction, B. P., 130-140" C./2'mm.,

11 1.4452, unreacted butyl fumarate as indicatcdby the refractive index. Therewas thus obtained as distillation residue 125.2 g. of an adduct, in which one mole of the methyl acetylricinoleate had combined with'an average of about 1.23 moles of butyl fumarate. The

residue is identified as adduct H in the plasticizer evaluations of Example 4.

Example 3 A mixture consisting of l32'g. (0.38 mole) of methyl acetylricionoleate and 203 g. (1.14 moles) of ethyl fumarate Was'heated in a nitrogen atmosphere at 223- 245- C. for about4.5 hours. Distillation of the resulting reaction product gave the following fractions:

, The residue (46 g.) was a light colored, highly viscous liquid, probably a mixture of adducts in which one mole of methyl acetylricinoleatewas combined with from 1 to 3 moles of the ethyl fumarate. Fraction IV is identified as adduct III and the residue as adduct IV in the plasticizer evaluations of Example 4.

Example 4 t Respective mixtures consisting of 60 parts by weight of polyvinyl chloride and 40 parts by weight of one of the adducts of Examples 1-3 were respectively milled to a homogeneous blend. During the milling there was observed substantially no. fuming and discoloration. Molded sheets of the respective'milled blends were clear, transparentandsubstantially, colorless. Testing of the 4 molded sheets by the testing procedures herein described gave the following values:

Low Tem- Vola- Hardness Solids Water perature tility, Loss, Ab- Adduct Flexibility, Per- Persorp- 0. cent Before After cent tion Vol. Vol. Per- Test Test cent minus 25.3... 1. 143 79 0. 03 0. 56 minus 37.0... 8. 9 77 77 0.09 O. 60 minus 32.5..- 5. 9 76 75 0. 18 0. 66 plus 4.4 0. 68 93 94 0. 02 0.68

The very good plasticizing action of the present alkyl acetylricinoleate-alkyl fumarate adducts is unexpected, for like testing of methyl and butyl acetylricinoleate showed these esters to be incompatible with polyvinyl chloride.

'While the above examples show only compositions in which the ratio of plasticizer to polymer content is 40:60, this ratio being employed in order to get comparable efficiencies, the content of adduct to polyvinyl chloride may be widely varied, depending upon the properties For many purposes a: plasticizer content, of say, from only 10 percent to 20 desired in the final product.

percent is preferred. The present polycarboxylates are compatible with polyvinyl chloride ,over wide ranges of concentrations, up ,to 50 percent of esters based on the total weight of the plasticized composition yielding desirable products.

Although the invention has been described particularly.

with reference to the use of the present adducts as plasticizers for polyvinyl chloride, these polycarboxylates are advantageously employed also as plasticizers for copolymers of vinyl chloride, for example, the copoly mers of vinyl chloride with vinyl acetate or vinylidene chloride, etc. Preferably such copolymers have a high vinyl chloride content, i. e., a vinyl chloride content of at least 70 percent by weight of vinyl chloride and up to 30 percent by weight of the copolymerizable monomer.

The plasticized polyvinyl halide compositions of the present invention have good thermal stability; however, for many purposes it may be advantageous to use known stabilizers in the plasticized compositions. Inasmuch as the present adducts are substantially unreactive with the.

commercially available heat and light stabilizers which are commonly employed with polyvinyl chloride, or. copolymers thereof, "the presence of such materials in the plasticized compositions does not impair the valuable.

properties of the adducts. The present polycarboxylates. are of general utility in softening vinyl chloride polymers. They may be used as the only plasticizing component in a compounded vinyl chloride polymer or they may be used in conjunction with other plasticizers.

WhatI claim is: 1. Polycarboxylates having the formula R!) EH00 OY HaCOOY' in which R,R, Y and Y' are alkyl radicals of from 1 to 5 carbon atoms, X is a mono-alkenyl radical of 10 1 carbon atoms and is a part of the acid portion of a ricinoleate and n is an integer of from 1 to 3.

2. A polycarboxylate having the formula omooo onooowmnon.

' CHJGOO(CH2)3CH3 in which n is an integer of 1 to 3 and X is a monoalkenyl radical of 10 carbon atoms and is a part of they acid portion of a ricinoleate.

3. A polycarboxylate having the formula CH3(CH)5CH.X.COOCE:

0112.000 CHCOO(CH2)3CH3 CHzCOO (OHmCHa in which n is an integer of 1 to 3 and X is a monoalkenyl radical of carbon atoms and is a part of the acid portion of a ricinoleate.

4. A polycarboxylate having the formula CHa(CH2)5CH.X.C O O CH:

CHsCO CHCOOCHzCHa HzCOOCH CH;

in which n is an integer of 1 to 3 and X is a monoalkenyl radical of 10 carbon atoms.

5. The method which comprises heating a dialkyl fumarate of from 6 to 14 carbon atoms with an alkyl acylricinoleate of the formula in which R and R are alkyl radicals of from 1 to 5 carbon atoms and recovering from the resulting reaction product an adduct in which one mole of said ricinoleate is combined with from 1 to 3 moles of said fumarate.

6. The method which comprises heating butyl acetylricinoleate with butyl fumarate and recovering from the resulting reaction product an adduct in which one mole 6 of said ricinoleate is combined with from 1 to 3 moles of said fumarate.

7. The method which comprises heating methyl acetylricinoleate with butyl fumarate and recovering from the resulting reaction product an adduct in which one mole References Cited in the file of this patent UNITED STATES PATENTS 1,927,295 Powers Sept. 19, 1933 2,023,995 DeGroote Dec. 10, 1935 2,188,888 Clocker Jan. 30, 1940 2,396,763 Ullmann Mar. 19, 1946 2,408,905 Black et al Oct. 8, 1946 2,526,395 Nichols Oct. 17, 1950 2,532,018 Floyd Nov. 28, 1950 2,598,635 Dazzi May 27, 1952 2,630,441 Dazzi Mar. 3, 1953 2,687,421 Butler Aug. 24, 1954 OTHER REFERENCES Pigman: Carbohydrate Chemistry," published by Academic Press, New York, N. Y., 1948 (page relied 

1. POLYCARBOXYLATES HAVING THE FORMULA 